Synthetic leather articles and methods for producing the same

ABSTRACT

Novel synthetic leather articles comprise a substrate and a coating applied to a surface of the substrate. The coating comprises a resin and a polymeric colorant. The polymeric colorant comprises a chromophore and an oligomeric constituent bound to the chromophore. Novel methods for producing synthetic leather articles using polymeric colorants are also provided.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.Ser. No. 11/395,665, filed on Mar. 31, 2006 now U.S. Pat. No. 7,662,461,the disclosure of which is hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention is directed to substrates comprising a coating onthe surface thereof, such as substrates having a coating thereonintended to mimic the look and feel of leather.

BACKGROUND OF THE INVENTION

Synthetic leather typically is produced by coating or laminating anelastic polymer resin, such as a polyurethane resin, a polyvinylchloride resin, or a blend of such resins, onto the surface of a fibrousbase material. In order to produce a synthetic leather in a variety ofcolors and/or shades, various pigments or dyes have been used to colorthe resin applied to the surface of the base material. However, the useof such pigments and dyes has not been without its disadvantages anddrawbacks.

For example, pigments usually have low tinting strength and a dullshade, which can limit the aesthetic qualities of synthetic leatherproduced using them. Pigments typically lack solubilizing groups, whichfrequently allows the pigment particles to aggregate and form largersecondary and tertiary aggregate particles during production processes.Owing to these difficulties, synthetic leathers colored withconventional pigments often exhibit poor color retention, have a dark ordull shade, or contain unsuitable variations in color depth. While theseproblems can be partially addressed through the addition of dispersingagents or by utilizing pigment dispersions, these measures often resultin increased production costs and still require great care to minimizecolor variations produced by settling of the pigment(s) and/orincompatibility of these components with the resin.

Dyes, on the other hand, typically contain solubilizing groups that canfacilitate dispersion of the dye in a suitable medium. Dyes alsotypically exhibit relatively high tinting strength, good transparency,good thermal stability, and acceptable resin compatibility.Nevertheless, dyes typically exhibit poor weather durability, poor waterresistance, poor oil resistance, and often migrate or bleed through tothe transfer substrates, such as a release paper, used to produce thesynthetic leather. In order to address the migration of dyes to thetransfer substrate, attempts have been made to utilize nylon orpolyurethane overcoats applied to the transfer substrate. However,satisfactory topcoats have not been developed without incurringsignificantly higher cost.

A need therefore remains for novel colored synthetic leather articlesthat address the deficiencies of articles produced with conventionalpigments and dyes, while still exhibiting the desired aestheticqualities. The present invention provides such articles and methods forproducing the same.

BRIEF SUMMARY OF THE INVENTION

A synthetic leather article comprises a substrate and a coating on atleast one surface of the substrate. The coating comprises a resin and apolymeric colorant. The polymeric colorant comprises a chromophore andan oligomeric constituent bound to the chromophore.

A method for producing a synthetic leather articles comprises the stepsof (a) providing a resin or prepolymer, (b) providing a polymericcolorant, (c) mixing the polymer colorant and the resin or prepolymer toform a mixture, (d) applying the mixture obtained in step (c) onto atransfer substrate and heating the substrate to dry the substrate andform a resin coating thereon, (e) applying an adhesive onto the resincoating produced in step (d), (f) applying a backing substrate to theadhesive layer produced in step (e), (g) heating the assembly producedin step (f) to dry the assembly and bond the fibrous backing substrateto the adhesive layer, and (h) removing the transfer substrate from theassembly produced in (g) to produce a synthetic leather article.

A method for producing a synthetic leather articles comprises the stepsof (a) providing a resin or prepolymer, (b) providing a polymericcolorant, (c) mixing the polymer colorant and the resin or prepolymer toform a mixture, (d) applying the mixture obtained in step (c) onto abacking substrate, (e) immersing the coated substrate obtained in step(d) in an aqueous solution to cure the resin or prepolymer and form acoating on the surface thereof, (f) removing the substrate from theaqueous solution, and (g) heating the substrate to dry the substrate andproduce a synthetic leather article.

DETAILED DESCRIPTION OF THE INVENTION

A synthetic leather article comprises a substrate and a coating on atleast one surface of the substrate. The coating comprises a resin and apolymeric colorant. The polymeric colorant can be dispersed within theresin or the polymeric colorant and the resin can be copolymerized toproduce a colored resin.

The substrate can be any suitable substrate, such as a fibroussubstrate. In certain possibly preferred embodiments, the substrate is atextile material. Suitable textiles include, but are not limited to,woven textiles, knit textiles, and non-wovens. The textiles can be madefrom any suitable natural fibers, synthetic fibers, or combinationsthereof.

In order to promote adhesion between the substrate and the coating, thesubstrate can comprise a precoat layer on the surface to which thecoating is applied. The precoat layer can comprise any suitablematerial, such as a material that promotes adhesion between thesubstrate and the coating. For example, the precoat layer can compriseelastomeric polymers.

The resin in the coating can be any suitable resin. The resin typicallywill be selected to provide an article that is flexible and durable,while providing the properties necessary or desirable for mimicking realleather. In certain possibly preferred embodiments, the resin isselected from the group consisting of polyurethane resins, polyurearesins, and combinations thereof. Suitable polyurethanes include linearpolyurethanes as well as cross-linked polyurethanes, such as apolyurethane cross-linked with hexamethylene diisocyanate trimer.

The resins suitable for use in the coating can be produced using anysuitable polyol. Suitable polyols include, but are not limited to,glycols of low molecular weight, such as ethylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,6-hexamethyleneglycol; polyester diols obtained from dibasic acids, such as adipicacid, maleic acid, and terephthalic acid; polyester diols, such aspolylactones obtained by subjecting lactones to ring-openingpolymerization with glycols; polycarbonate diols; and polyether diols,such as polytetramethylene glycol, polyethylene glycol, andpolypropylene glycol.

The resins suitable for use in the coating can be produced using anysuitable isocyanate. Suitable isocyanates include, but are not limitedto, aromatic diisocyanates, such as toluene-2,4-diisocyanate (TDI),4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylenediisocyanate, 4-chloro-1,3-phenylene diisocyanate,4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether,4,4′-methylenebis(phenyl-isocyanate) (MDI), polymeric MDI, durylenediisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI),1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidinediisocyanate, and 4,4-diisocyanatodibenzyl; aliphatic diisocyanates,such as methylene diisocyanate, 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate;alicyclic diisocyanates, such as 1,4-cyclohexylene diisocyanate,4,4-methylene-bis(cyclohexylisocyanate), 1,5-tetrahydronaphthalenediisocyanate, isophorone diisocyanate, hydrogenated MDI, andhydrogenated XDI; and polyurethane prepolymers obtained by reacting anyof the aforementioned diisocyanates with polyols or polyamines of lowmolecular weights such that the resulting prepolymers have isocyanategroups at ends thereof. Among the aforementioned, aromaticdiisocyanates, particularly diphenylmethane-4,4′-diisocyante (4,4′-MDI)or polymeric MDI, are preferred for obtaining articles exhibiting goodphysical characteristics such as thermal stability, solution stability,and fracture strength. Alicyclic diisocyanates, such as isophorones, arepreferred for obtaining polyurethanes that exhibit anti-yellowingproperties and are not easily discolored upon exposure to sunlight.

The resins or prepolymers suitable for use in the coating can beproduced using suitable chain extenders. These include, but are notlimited to, water; low-molecular diols, such as ethylene glycol andpropylene glycol; aliphatic diamines, such as ethylenediamine; aromaticdiamines, such as 4,4′-diaminodiphenylmethane; alicyclic diamines, suchas 4,4′-diaminodicyclohexylmethane and isophoronediamine; alkanolamines,such as ethanolamine; hydrazines; and dihydrazides, such as succinicdihydrazide. Among the aforementioned chain extenders, the diaminecompounds are preferable, with 4,4′-diaminodiphenylmethane beingparticularly preferred due to its heat resistance and4,4′-diaminodicyclohexylmethane being preferred for light resistance.The aforementioned chain extenders can, of course, be used alone or inany suitable combination.

Other resins or polymers can be used in combinations with theaforementioned resins. Thus, in certain embodiments, the coating cancomprise one or more polymers or resins selected from the groupconsisting of polyvinyl chloride (PVC), polyvinylidene chloride,polyvinyl acetate, polyacrylic acid, alkylpolyacrylate, polymethacrylicacid, alkylpolymethacrylate, and copolymers thereof.

The colorant in the coating can be any suitable polymeric colorant. Asutilized herein, the term “polymeric colorant” is used to refer to acolorant comprising a chromophore and an oligomeric constituent bound tothe chromophore. The oligomeric constituent can be bound to thechromophore via any suitable means, such as a covalent bond, an ionicbond, or suitable electrostatic interaction. The oligomeric constituentcan have any suitable formula weight. As utilized herein in reference tothe oligomeric constituent, the term “formula weight” refers to theweight (in grams) of the oligomeric constituent per mole of thepolymeric colorant. In other words, the “formula weight” of theoligomeric constituent refers to the portion of the polymeric colorant'smolecular weight attributable to the oligomeric constituent (theremainder being attributable to the chromophore and any groups attachedthereto). Typically, the oligomeric constituent has a formula weight ofabout 40 or more. The oligomeric constituent typically has a formulaweight of about 3,000 or less. In certain possibly preferredembodiments, the oligomeric constituent has a formula weight of about 40to about 3,000.

Suitable polymeric colorants include, but are not limited to, thosepolymeric colorants conforming to structure (I) or structure (III)

In structure (I), R₁ or R₁-E together represents an organic chromophore.E is a linking moiety selected from the group consisting of nitrogen,oxygen, sulfur, a sulfite group, a sulfonamide group, and a carboxylgroup. Also, n and m are independently selected from the groupconsisting of integers between 1 and 5. In structure (III), R₄ orR₄(G)_(h) represents an organic chromophore. G is selected from thegroup consisting of SO₃ ⁻ (a sulfite anion) and CO₂ ⁻ (a carboxylateanion). Each R₅ is independently selected from the group consisting ofhydrogen, alkyl groups, and aryl groups, and M is selected from thegroup consisting of nitrogen atoms and phosphorous atoms. Also, h is aninteger between 1 and 4, k is an integer between 0 and 5, and j is aninteger between 1 and 6. The sum of k and j is equal to 4 when M is anitrogen atom, and the sum of k and j is equal to 6 when M is aphosphorous atom.

In each of structures (I) and (III), X is an end group independentlyselected from the group consisting of hydrogen, hydroxyl groups, thiolgroups, amine groups, alkyl groups, aryl groups, alkyl ester groups,aryl ester groups, organic sulfonate groups, organic sulfate groups, andamide groups. Also, each Z in the structures is an oligomericconstituent independently selected from the group consisting of (i)oligomers comprising at least three monomers selected from the groupconsisting of C₂-C₂₀ alkyleneoxy groups, glycidol groups, and glycidylgroups, (ii) aliphatic oligomeric esters conforming to structure (II)

and (iii) combinations of (i) and (ii). In structure (II), R₂ and R₃ areindependently selected from the group consisting of hydrogen and C₁-C₁₀alkyl groups, f is an integer between 1 and 10, and g is any positiveinteger or fraction between 1 and 20. As will be understood by those ofordinary skill in the art, suitable values for g include both integersand fractions because the length of the oligomeric constituent on thepolymeric colorant molecules may vary. Thus, the value for g representsan average length of the ester chain for a given sample or collection ofpolymeric colorant molecules.

An example of suitable polymeric colorants conforming to structure (I)include methine-based colorants, such as those colorants conforming tostructure (IV)

In structure (IV), R₆ is selected from the group consisting of hydrogen,alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, andoligomeric constituents having the structure —Z—X. Each R₇ isindependently selected from the group consisting of hydrogen, halogenatoms, alkyl groups, alkoxy groups, nitrile groups, nitro groups, amidegroups, and sulfonamide groups, and q is an integer between 0 and 4. R₈and R₉ are independently selected from the group consisting of hydrogen,halogen atoms, tertiary amino groups, imine groups, cyano groups,pyridinium groups, ester groups, amide groups, sulfate groups, sulfonategroups, sulfide groups, sulfoxide groups, phosphine groups, phosphiniumgroups, phosphate groups, nitrile groups, mercapto groups, nitro groups,sulfone groups, acyl groups, azo groups, alkyl groups, alkoxy groups,aryl groups, aryloxy groups, arylalkyl groups, arylalkoxy groups,alkylaryl groups, and alkylaryloxy groups.

More specific examples of methine-based polymeric colorants suitable foruse in the synthetic leather articles include those polymeric colorantsconforming to structure (IX)

In structure (IX), R₂₆ is selected from the group consisting of cyanogroups, nitro groups, alkylcarbonyl groups, arylalkylcarbonyl groups,alkoxycarbonyl groups, arylalkoxycarbonyl groups, amide groups, andalkylamide groups. R₂₇ is selected from the group consisting ofhydrogen, C₁-C₂₀ alkyl groups, and C₇-C₂₀ arylalkyl groups. R₂₈ isselected from the group consisting of hydrogen, C₁-C₂₀ alkyl groups,aryl groups, C₇-C₂₀ arylalkyl groups, C₇-C₂₀ alkylaryl groups, andoligomeric constituents having the structure —Z—X. Z is an oligomericconstituent comprising at least three monomers selected from the groupconsisting of C₂-C₂₀ alkyleneoxy groups (e.g., ethylene oxide, propyleneoxide, butylene oxide), glycidol groups, and glycidyl groups. In certainpossibly preferred embodiments of the methine-based colorants conformingto structure (IX), R₂₆ is a cyano group or a C₁-C₁₀ alkylcarbonyl group,R₂₇ is hydrogen or a methyl group, R₂₈ is an oligomeric constituenthaving the structure —Z—X, and Z is an oligomeric constituent comprisingat least three monomers selected from the group consisting of C₂-C₂₀alkyleneoxy groups (e.g., ethylene oxide, propylene oxide, butyleneoxide), glycidol groups, and glycidyl groups.

Another example of suitable polymeric colorants conforming to structure(I) include azo-based colorants, such as those colorants conforming tostructure (V)

In structure (V), R₁₀ is selected from the group consisting of hydrogen,alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, andoligomeric constituents having the structure —Z—X. Each R₁₁ isindependently selected from the group consisting of hydrogen, halogenatoms, alkyl groups, alkoxy groups, nitrile groups, nitro groups, amidegroups, and sulfonamide groups, and q is an integer between 0 and 4. R₁₂is selected from the group consisting of aromatic groups andheteroatom-containing aromatic groups. Q is hydrogen or a linking groupselected from the group consisting of oxygen, sulfur, a carbonyl group,a sulfonyl group, a C₁-C₈ alkyl group, a C₂-C₈ alkene group, ap-phenylenediamine group, a m-hydroxybenzene group, and a m-di(C₁-C₄)alkoxybenzene, and r is equal to 1 or 2.

More specific examples of azo-based polymeric colorants suitable for usein the synthetic leather articles include those polymeric colorantsconforming to structure (X)

In structure (X), R₂₉ is selected from the group consisting of aromaticgroups and heteroatom-containing aromatic groups. R₃₀ is selected fromthe group consisting of hydrogen, C₁-C₂₀ alkyl groups, and C₇-C₂₀arylalkyl groups. R₃₁ is selected from the group consisting of hydrogen,C₁-C₂₀ alkyl groups, aryl groups, C₇-C₂₀ arylalkyl groups, C₇-C₂₀alkylaryl groups, and oligomeric constituents having the structure —Z—X.Z is an oligomeric constituent comprising at least three monomersselected from the group consisting of C₂-C₂₀ alkyleneoxy groups (e.g.,ethylene oxide, propylene oxide, butylene oxide), glycidol groups, andglycidyl groups. In certain possibly preferred embodiments of theazo-based colorants conforming to structure (X), R₂₉ is an aromaticgroup or a heteroatom-containing aromatic group, R₃₀ is a hydrogen or amethyl group, R₃₁ is an oligomeric constituent having the structure—Z—X, and Z is an oligomeric constituent comprising at least threemonomers selected from the group consisting of C₂-C₂₀ alkyleneoxy groups(e.g., ethylene oxide, propylene oxide, butylene oxide), glycidolgroups, and glycidyl groups.

Azo-based colorants suitable for use in the synthetic leather articlesinclude bisazo-based colorants such as those conforming to structure(XI)

In structure (XI), W is a linking group and is selected from the groupconsisting of oxygen, sulfur, a sulfone group, a carbonyl group, C₁-C₈alkyl groups, C₂-C₈ alkylene groups, and p-phenylenediamine. R₃₂ isselected from the group consisting of hydrogen, C₁-C₂₀ alkyl groups, andC₇-C₂₀ arylalkyl groups. R₃₃ is selected from the group consisting ofhydrogen, C₁-C₂₀ alkyl groups, aryl groups, C₇-C₂₀ arylalkyl groups,C₇-C₂₀ alkylaryl groups, and oligomeric constituents having thestructure —Z—X. Z is an oligomeric constituent comprising at least threemonomers selected from the group consisting of C₂-C₂₀ alkyleneoxy groups(e.g., ethylene oxide, propylene oxide, butylene oxide), glycidolgroups, and glycidyl groups. In certain possibly preferred embodimentsof the bisazo-based colorants conforming to structure (XI), W is asulfone group, R₃₂ is hydrogen or a methyl group, R₃₃ is an oligomericconstituent having the structure —Z—X, and Z is an oligomericconstituent comprising at least three monomers selected from the groupconsisting of C₂-C₂₀ alkyleneoxy groups (e.g., ethylene oxide, propyleneoxide, butylene oxide), glycidol groups, and glycidyl groups.

Suitable polymeric colorants conforming to structure (I) also includetriphenylmethane-based colorants, such as those colorants conforming tostructure (VI)

R₁₃ is selected from the group consisting of hydrogen, alkyl groups,aryl groups, arylalkyl groups, alkylaryl groups, and oligomericconstituents having the structure —Z—X. R₁₄ is selected from the groupconsisting of hydrogen, halogen atoms, alkyl groups, alkoxy groups,alkylamino groups, and arylamino groups. R₁₅ is selected from the groupconsisting of hydrogen, halogen atoms, alkyl groups, alkoxy groups,alkylamino groups, arylamino groups, cyano groups, nitro groups, amidegroups, sulfite groups, and sulfonamide groups, and each q is an integerbetween 0 and 4.

More specific examples of triphenylmethane-based polymeric colorantssuitable for use in the synthetic leather articles include thosepolymeric colorants conforming to structure (XII)

In structure (XII), R₃₅ is selected from the group consisting ofhydrogen, halogen atoms, alkyl groups, alkoxy groups, alkylamino groups,and arylamino groups. R₃₄ is selected from the group consisting ofhydrogen, alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups,and oligomeric constituents having the structure —Z—X. Alternatively,R₃₅ can be joined to R₃₄ to form a ring. Z is an oligomeric constituentcomprising at least three monomers selected from the group consisting ofC₂-C₂₀ alkyleneoxy groups (e.g., ethylene oxide, propylene oxide,butylene oxide), glycidol groups, and glycidyl groups. In certainpossibly preferred embodiments of the triphenylmethane-based colorantsconforming to structure (XII), R₃₅ is hydrogen, R₃₄ is an oligomericconstituent having the structure —Z—X, and Z is an oligomericconstituent comprising at least three monomers selected from the groupconsisting of C₂-C₂₀ alkyleneoxy groups (e.g., ethylene oxide, propyleneoxide, butylene oxide), glycidol groups, and glycidyl groups.

Suitable polymeric colorants conforming to structure (I) further includebenzodifuranone-based colorants, such as those colorants conforming tostructure (VII)

In structure (VII), Y is selected from the group consisting of oxygen,sulfur, and NR₄₀, where R₄₀ is selected from the group consisting ofhydrogen, alkyl groups, and aryl groups. R₁₆ and R₁₇ are independentlyselected from the group consisting of hydrogen, halogen atoms, hydroxylgroups, alkyl groups, alkenyl groups, and alkoxy groups. R₁₈, R₁₉, R₂₀,R₂₁, and R₂₂ are independently selected from the group consisting ofhydrogen, halogen atoms, C₁-C₂₀ alkyl groups, C₁-C₂₀ alkylester groups,hydroxyl groups, thio groups, cyano groups, sulfonyl groups, sulfogroups, sulfato groups, aryl groups, nitro groups, carboxyl groups,C₁-C₂₀ alkoxy groups, C₁-C₂₀ alkylamino groups, acrylamino groups,C₁-C₂₀ alkylthio groups, C₁-C₂₀ alkylsulfonyl groups, C₁-C₂₀ alkylphenylgroups, phosphonyl groups, C₁-C₂₀ alkylphosphonyl groups, C₁-C₂₀alkoxycarbonyl groups, phenylthio groups, and oligomeric constituentshaving the structure -E-(Z—X)_(n). At least one of R₁₈, R₁₉, R₂₀, R₂₁,and R₂₂ is an oligomeric constituent having the structure -E-(Z—X)_(n).

More specific examples of benzodifuranone-based polymeric colorantssuitable for use in the synthetic leather articles include thosepolymeric colorants conforming to structure (XIII)

In structure (XIII), R₃₆ is selected from the group consisting ofhydrogen, alkyl groups, aryl groups, arylalkyl groups, alkylaryl groups,and oligomeric constituents having the structure —Z—X. R₃₇ is selectedfrom the group consisting of hydrogen, halogen atoms, alkoxy groups,alkylamino groups, and a groups having the structure —R₄₁—C(O)—NH—,where R₄₁ is selected from the group consisting of hydrogen, alkylgroups, and aryl groups. Z is an oligomeric constituent comprising atleast three monomers selected from the group consisting of C₂-C₂₀alkyleneoxy groups (e.g., ethylene oxide, propylene oxide, butyleneoxide), glycidol groups, and glycidyl groups. In certain possiblypreferred embodiments of the benzodifuranone-based colorants conformingto structure (XIII), R₃₇ is hydrogen or a methyl group, R₃₆ is anoligomeric constituent having the structure —Z—X, and Z is an oligomericconstituent comprising at least three monomers selected from the groupconsisting of C₂-C₂₀ alkyleneoxy groups (e.g., ethylene oxide, propyleneoxide, butylene oxide), glycidol groups, and glycidyl groups.

Another example of suitable polymeric colorants conforming to structure(I) include anthraquinone-based colorants, such as those colorantsconforming to structure (VIII)

In structure (VIII), R₂₃ is selected from the group consisting ofhydrogen, halogen atoms, hydroxyl groups, amine groups, nitro groups,and acetamide groups. R₂₄ and R₂₅ are independently selected from thegroup consisting of hydrogen and hydroxyl groups, and A is selected fromthe group consisting of alkyl groups and aryl groups. B is selected fromthe group consisting of groups conforming to structure (XV) andstructure (XVI)

In structure (XV), R₃₈ is selected from the group consisting ofhydrogen, C₁-C₁₈ alkyl groups, and aryl groups. In structure (XVI), R₃₉is selected from the group consisting of aryl groups and oligomericconstituents having the structure -A-Z—X.

More specific examples of anthraquinone-based polymeric colorantssuitable for use in the synthetic leather articles include thosepolymeric colorants conforming to structure (XIV)

In structure (XIV), A is selected from the group consisting of alkylgroups and aryl groups, and B is selected from the group consisting ofgroups conforming to structure (XV) and structure (XVI)

In structure (XV), R₃₈ is selected from the group consisting ofhydrogen, C₁-C₁₈ alkyl groups, and aryl groups. In structure (XVI), R₃₉is selected from the group consisting of aryl groups and oligomericconstituents having the structure -A-Z—X. In certain possibly preferredcolorants conforming to structure (XIV), A is selected from the groupconsisting of alkyl groups and aryl groups, and B is a group having thestructure —NH—R₃₉.

Suitable polymeric colorants conforming to structure (III) includephthalocyanine-based polymeric colorants in which R₄ is a metalphthalocyanine derivative. In certain possibly preferred embodiments ofthe polymeric colorants conforming to structure (III), R₄ is a copperphthalocyanine chromophore, G is a sulfite group, h, j, and k are equalto 2, R₅ is a C₁-C₂₀ alkyl group, M is a nitrogen, and Z is anoligomeric constituent comprising at least three monomers selected fromthe group consisting of C₂-C₂₀ alkyleneoxy groups (e.g., ethylene oxide,propylene oxide, butylene oxide), glycidol groups, and glycidyl groups.

The selection of a suitable polymeric colorant can be based on severalfactors. For example, when the polymeric colorant is used to produce acolored polyurethane prepolymer, the polymeric colorant preferablycomprises oligomer or polymer chains that terminate with groupscontaining active hydrogen, such as a hydroxyl group, a thiol group, oran amine group. This active hydrogen allows such polymeric colorants tobe reacted with a suitable isocyanate-containing compound, therebyproducing a colored prepolymer. This colored prepolymer can then befurther reacted to produce a colored synthetic leather article accordingto the invention. When directly used with polyurethane resin solution ordispersion to produce synthetic leather, the compatibility of thepolymeric colorant with the resin is more important than the reactivityof polymer chain terminal groups. In other words, the terminal group Xis not believed to be critical with regard to the functioning of thepolymeric colorant when the polymeric colorant is merely dispersed inthe resin of the synthetic leather article.

The polymeric colorants can be present in the synthetic leather articlesof the invention in any suitable amount. Generally, the amount of thepolymeric colorants employed in a colored polyurethane prepolymer orsynthetic leather article depends upon the desired shade and depth ofcolor. Other factors may include whether or not other coloring agentsare employed, such as dyes and/or pigments. When used to producepolyurethane prepolymers, the molar ratio of isocyanate/OH from thepolymeric colorant(s) needs to be taken into account to adjust theloading of polyols since some polymeric colorants contain hydroxylgroup(s). Another factor to consider is whether the polymeric colorantsare used in the base layers or the skin coat layer. The amount of thepolymeric colorant(s) employed is not limited to a specific weightrange. However, to produce a colored polyurethane prepolymer, thepolymeric colorant(s) can be used in an amount of about 0.01 to 40% byweight, and may also be in the range of about 0.1 to about 15% byweight, with respect to the requirement of targeted color shade or depthor physical properties of the prepolymer to be made. To produce coloredsynthetic leather compositions using uncolored commercial prepolymers,the polymeric colorant(s) can be used in an amount of about 0.01 to 15%by weight, preferably 0.1 to 5% by weight, depending upon thecompatibility of the polymeric colorant with the polyurethane resin, andcolor shade and depth desired for the leather article.

The flexibility of the oligomer or polymer chain(s) of the polymericcolorants may be designed or modified to be compatible with almost anypolymer resins and prepolymers, thus enabling a wide selection ofisocyanates and polyols to be chosen to make polyurethane/polyurearesins or prepolymers, and/or other elastic polymers to be used withpolyurethane/polyurea resins to achieve desired physical or chemicalproperties for the colored synthetic leather articles. Colored syntheticleather articles containing polymeric colorants generally exhibit low tono bleeding and migration, for example, to the release paper. While notwishing to be bound to any particular theory, this is believed to be dueto either the compatibility between the colorants and the resin(s)employed or covalent bonding of the polymeric colorant(s) with theresin. The liquid or paste nature of the polymeric colorants may alsofacilitate the colored synthetic leather manufacturing process byeliminating the problems associated with handling large amounts ofsolids, such as the pigments typically used to produce syntheticleathers. The polymeric colorants' liquid or paste nature andcompatibility with the resins may also shorten the amount of time neededto satisfactorily mix the colorants with the resins or prepolymers, ascompared to the mixing times required when dyes or pigments are used.

The inherent characteristics of the polymeric colorants, such as theliquid or paste nature and the compatibility of the polymeric colorantswith each other, may enable one to freely blend several differentpolymeric colorants in several different amounts, without the need touse external solvents. The ability to freely blend the polymericcolorants can enable one to produce almost any desirable color shades,which are otherwise extremely difficult to achieve using conventionaldyes or pigments. Thus, for example, by using only 5 polymericcolorants, such as a yellow colorant, an orange colorant, a redcolorant, a violet colorant, and a blue colorant, one can achieve a muchbroader color space than that produced using conventional dyes and/orpigments. In one scenario, for example, a synthetic leather manufacturerneed only stock 5 different polymeric colorants to produce a widevariety of desired color shades and brightness for synthetic leatherarticles. Thus, the inherent characteristics of the polymeric colorantsmay enable the colored synthetic leather articles according to theinvention to achieve a much broader and/or brighter color shade thanthose previously obtained using conventional dyes and/or pigments.

Furthermore, the relatively high water solubility of the polymericcolorants may enable the manufacturing equipment used to produce asynthetic leather article according to the invention to be cleaned moreeasily than equipment used to produce synthetic leather usingconventional dyes and/or pigments. This easy clean-up may enable thesynthetic leather articles according to the invention to be produced ina more cost effective manufacturing process as compared to conventionalmanufacturing processes using conventional dyes and/or pigments.

In addition to the above-described polymeric colorants, other coloringagents can be incorporated into the synthetic leather article in orderto control the color hue. These coloring agents include conventionallyknown pigments and dyes. Examples of blue pigments include, but are notlimited to, phthalocyanine C.I. Pigment Blue 15:3 and indanthrone C.I.Pigment Blue 60; examples of red pigments include, but are not limitedto, quinacridone C.I. Pigment Red 122, azo C.I. Pigment Red 22, C.I.Pigment Red 48:1, C.I. Pigment Red 48:3 and C.I. Pigment Red 57:1;examples of yellow pigments include, but are not limited to, azo C.I.Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I.Pigment Yellow 17, C.I. Pigment Yellow 97, C.I. Pigment Yellow 155,benzimidazolone C.I. Pigment Yellow 151, C.I. Pigment Yellow 154 andC.I. Pigment Yellow 180; examples of black pigments include, but are notlimited to, carbon black. Examples of suitable dyes include, but are notlimited to, solvent dyes, such as Yellow 82, Orange 5, Orange 62, Red 8,Red 62, Red 122, Blue 70, Black 27, and Black 34. For ease of handlingand mixing in the production of the synthetic leather articles, anypigments used preferably are in added in the form of a dispersion or inresin pallet/flake forms, and any dyes used preferably are added in theform of a in solution or in resin pallet/flake forms.

The synthetic leather articles of the invention can be produced usingany suitable method. For example, the synthetic leather articles can beproduced using both “a direct coating process” and “a transfer coatingprocess”, or “dry” and “wet” methods. In two-component technologies,polymeric colorants preferably are mixed with polyols to react withisocyanates to form a high viscosity isocyanate- or hydroxyl-terminatedprepolymer. This prepolymer can then be directly coated onto a substrateor onto transfer substrate (e.g., release paper) using a doctor bladeand cured by respective curing methods. If a free resin film isproduced, the film then needs to be laminated to a textile substrate ina subsequent step. In one-component technologies using commerciallyavailable polyurethane or polyurea resins, the resin can be used in theform of a solvent solution (“solvent method”), or the resin can be inthe form of an aqueous dispersion (“aqueous method”). In the solventmethod, the polymeric colorant(s) preferably are thoroughly mixed with apolyurethane solution in polar solvents, such as dimethylformamide (DMF)and/or methyl ethyl ketone (MEK). The high viscosity solution is thenspread onto a carrier or release paper, and the material is oven driedand laminated onto a substrate to form a synthetic leather article. Inthe aqueous method, the polymeric colorant(s) preferably are thoroughlymixed with an aqueous polyurethane dispersion (PUD) to form an aqueousemulsion. A suitable substrate is then impregnated with the emulsion,and the coated substrate is dried and cured to produce a syntheticleather article.

In a first method embodiment, the invention provides a method forproducing a synthetic leather article comprising the steps of (a)providing a resin or prepolymer, (b) providing a polymeric colorant, (c)mixing the polymer colorant and the resin or prepolymer to form amixture, (d) applying the mixture obtained in step (c) onto a transfersubstrate and heating the substrate to dry the substrate and form aresin coating thereon, (e) applying an adhesive onto the resin coatingproduced in step (d), (f) applying a backing substrate to the adhesivelayer produced in step (e), (g) heating the assembly produced in step(f) to dry the assembly and bond the fibrous backing substrate to theadhesive layer, and (h) removing the transfer substrate from theassembly produced in (g) to produce a synthetic leather article.

The substrate, resin or prepolymer, and polymeric colorant used in thefirst method embodiment can be any suitable substrate, resin orprepolymer, and polymeric colorant, including those described above withrespect to the synthetic leather articles according to the invention.The transfer substrate used in the first method embodiment can be anysubstrate that permits the formation of a resin coating thereon, whilestill enabling that resin coating to be released from the substratewithout damaging the coating. Suitable transfer substrates include, butare not limited to, a release paper, such as a silicone-treated,mirror-surface release paper.

In accordance with the first method embodiment, a synthetic leatherarticle can be produced, for example, by thoroughly mixing apolyurethane resin solution in methyl ethyl ketone/dimethylformamidewith at least one polymeric colorant and, optionally, with otheradditives. The mixture is then directly coated onto a release paper.After evaporating the solvent by oven drying or other drying process toproduce a resin coating on the release paper, a thin layer of adhesiveis applied onto the resin coating. A suitable substrate is then appliedto the adhesive layer, and the resulting assembly is heated. The releasepaper is then peeled off of the assembly to reveal a synthetic leatherarticle. Furthermore, due to the lack of or minimal color migrationresulting from the use of the polymeric colorants, the release papertypically is not discolored by the colorants employed and, therefore,can be reused.

In a second method embodiment, the invention provides a method forproducing a synthetic leather article comprising the steps of (a)providing a resin or prepolymer, (b) providing a polymeric colorant, (c)mixing the polymer colorant and the resin or prepolymer to form amixture, (d) applying the mixture obtained in step (c) onto a backingsubstrate, (e) immersing the coated substrate obtained in step (d) in anaqueous solution to cure the resin or prepolymer and form a coating onthe surface thereof, (f) removing the substrate from the aqueoussolution, and (g) heating the substrate to dry the substrate and producea synthetic leather article.

The substrate, resin or prepolymer, and polymeric colorant used in thesecond method embodiment can be any suitable substrate, resin orprepolymer, and polymeric colorant, including those described above withrespect to the synthetic leather articles according to the invention.

In accordance with the second method embodiment, a synthetic leatherarticle can be produced, for example, by thoroughly mixing apolyurethane resin or prepolymer solution in dimethylformamide with atleast one polymeric colorant and, optionally, with other additives. Themixture is then coated onto a suitable substrate, and the coatedsubstrate is then immersed in an aqueous medium. While immersed in theaqueous medium, the solvent (e.g., dimethylformamide) is extracted fromthe mixture, which causes the polymer in the mixture to coagulate andform a film. The resulting substrate is then dried to produce asynthetic leather article.

The following examples further illustrate the invention but, of course,should not be construed as in any way limiting its scope.

EXAMPLE 1

This example demonstrates the production of a synthetic leather articlein accordance with the invention. 70 parts (0.14 mol) of Fomrez®polyester polyol (available from Witco) having a molecular weight of 500and an OH number of 225, 48 parts (0.04 mol) of Millijet® Red 17polymeric colorant (available from Milliken Chemical) which had beendiluted to a color value of 30 abs./g/L, 32 parts (0.36 mol) of1,4-butyleneglycol, and 374 parts of dimethylformamide (DMF) werecharged into a 3-neck flask equipped with a reflux condenser, amechanical stirrer, and a thermo-controller. With vigorous stirring, 136parts (0.54 mol) of diphenylmethane-4,4′-diisocyanate was slowly added.After stirring for 15 minutes, 300 parts of DMF was added and the wholemixture was then heated to approximately 90-100° C. for 1.5 hours tocomplete the reaction. The resulting product was then diluted with DMFto form a red viscous polyurethane solution having a 25% solids content.

The red polyurethane solution was then applied to a commerciallyavailable fabric substrate to form a coating of the substrate having athickness of 2 mm. The coated substrate was then soaked in an aqueousbath containing 4% by weight of DMF and kept at 30° C. for 5 minutes tocoagulate the coating layer. The coated fabric was then soaked in warmwater at approximately 50-60° C. for 40 minutes to extract the DMF,squeezed and dried at 100° C. for 20 minutes. A red synthetic leatherwas obtained.

EXAMPLE 2

This example demonstrates the production of a synthetic leather articlein accordance with the invention. The procedure of Example 1 wasrepeated except that the red polymeric colorant was replaced with 60parts of Millijet® Violet 82 polymeric colorant (available from MillikenChemical) which had been diluted to a color value of 24 abs./g/L. Theprocess produced a violet synthetic leather.

EXAMPLE 3

This example demonstrates the production of a synthetic leather articlein accordance with the invention. The procedure of Example 1 wasrepeated except that the Fomrez® polyester polyol was replaced with 74parts of Tone® Polyol 0201 polyester polyol (available from Dow), whichhad a molecular weight of 530 and an OH number of 210. The redpolyurethane solution obtained had a solids content of 25%, and theprocess produced a red synthetic leather.

EXAMPLE 4

This example demonstrates the production of a synthetic leather articlein accordance with the invention. The procedure of Example 3 wasrepeated except that the red polymeric colorant was replaced with 60parts of Millijet® Violet 82 polymeric colorant (available from MillikenChemical) which had been diluted to a color value of 24 abs./g/L. Theprocess produced a violet synthetic leather.

EXAMPLE 5

This example demonstrates the production of a synthetic leather articlein accordance with the invention. The procedure of Example 1 wasrepeated except that the Fomrez® polyester polyol was replaced with 116parts of Tone® Polyol 0210 polyester polyol (available from Dow), whichhad a molecular weight of 830 and an OH number of 135. The redpolyurethane solution obtained had a solids content of 25%, and theprocess produced a red synthetic leather.

EXAMPLE 6

This example demonstrates the production of synthetic leather articlesin accordance with the invention. 70 parts (0.14 mol) of Fomrez®polyester polyol (available from Witco) having a molecular weight of 500and an OH number of 225, 48 parts (0.04 mol) of Millijet® Red 17polymeric colorant (available from Milliken Chemical) which had beendiluted to a color value of 30 abs./g/L, 32 parts (0.36 mol) of1,4-butyleneglycol, and 374 parts of dimethylformamide (DMF) werecharged into a 3-neck flask equipped with a reflux condenser, amechanical stirrer, and a thermo-controller. With vigorous stirring, 152parts (0.61 mol) of diphenylmethane-4,4′-diisocyanate was slowly added(the [NCO]/[OH] ratio being 1.12). After stirring for 15 minutes, 300parts of DMF was added and the whole mixture was then heated toapproximately 90-100° C. for 1.5 hours to complete the reaction. Theresulting product was then diluted with DMF to form a red viscouspolyurethane resin/prepolymer solution having a 25% solids content and a12.2% (molarity) excess of free isocyanate.

In a first method for producing a synthetic leather article, the redpolyurethane resin/prepolymer solution was directly applied onto acommercially available silicone-treated, mirror-surface release paper toform a film coating having a thickness of approximately 15 microns. Acommercially available base substrate having a thickness of 1 mm (anon-woven fibrous sheet having a thickness of 80 microns and apolyurethane elastomer impregnated/coated and solidified on one side)was then pressed/bonded onto this film coating. Then, the assembly washeated to a temperature of approximately 120° C. in an oven and kept atthat temperature for 3 minutes. The assembly was then removed from theoven and cooled down to room temperature, and the release paper was thenpeeled off of the assembly. A synthetic leather article having a redskin layer was thus obtained. Furthermore, no visible red color wasdetected on the release paper, which suggests that none of the redcolorant had migrated onto the release paper.

In a second method for producing a synthetic leather article, the redpolyurethane resin/prepolymer solution was applied to a commerciallyavailable fabric substrate to form a film coating having a thickness of2 mm. The coated substrate was then soaked in an aqueous bath containing4% by weight of DMF and kept at 30° C. for 5 minutes to coagulate thecoating layer. The coated fabric was then soaked in warm water at 50-60°C. for 40 minutes to extract the DMF, squeezed and dried at 100° C. for20 minutes. A red synthetic leather was obtained.

EXAMPLE 7

This example demonstrates the production of synthetic leather articlesin accordance with the invention. The procedure of Example 6 wasfollowed except that the Fomrez® polyester polyol was replaced with 74parts of Tone® Polyol 0201 polyester polyol (available from Dow), whichhad a molecular weight of 530 and an OH number of 210. A red, viscouspolyurethane resin/prepolymer solution having a 25% solids content and a12.2% (molarity) excess of free isocyanate was obtained.

The resulting polyurethane resin/prepolymer solution was then used toproduce red synthetic leather articles in accordance with the first andsecond methods described in Example 6. As in the first method describedin Example 6, the release paper used to produce the synthetic leatherarticle did not show visible signs of color migration.

EXAMPLE 8

This example demonstrates the production of synthetic leather articlesin accordance with the invention. The procedure of Example 6 wasfollowed except that the Fomrez® polyester polyol was replaced with 116parts of Tone® Polyol 0210 polyester polyol (available from Dow), whichhad a molecular weight of 830 and an OH number of 135. The red, viscouspolyurethane resin/prepolymer solution obtained had a solids content of25% and a 12.2% (molarity) excess of free isocyanate.

The resulting polyurethane resin/prepolymer solution was then used toproduce red synthetic leather articles in accordance with the first andsecond methods described in Example 6. As in the first method describedin Example 6, the release paper used to produce the synthetic leatherarticle did not show visible signs of color migration.

EXAMPLE 9

This example demonstrates the production of a synthetic leather articlein accordance with the invention. 74 parts (0.14 mol) of Tone® 0201polyester polyol (available from DOW) having a molecular weight of 530and an OH number of 210, 48 parts (0.04 mol) of Millijet® Red 17polymeric colorant (available from Milliken Chemical) which had beendiluted to a color value of 30 abs./g/L, 32 parts (0.36 mol) of1,4-butyleneglycol, and 374 parts of dimethylformamide (DMF) werecharged into a 3-neck flask equipped with a reflux condenser, amechanical stirrer, and a thermo-controller. With vigorous stirring, 152parts (0.61 mol) of diphenylmethane-4,4′-diisocyanate was slowly added(the [NCO]/[OH] ratio being 1.12). After stirring for 15 minutes, 300parts of DMF was added and the whole mixture was then heated toapproximately 90-100° C. for 1.5 hours to complete the reaction. Afterthe mixture had cooled to approximately 70° C., a solution containing2.2 parts of methanol in 10 parts DMF was added to the mixture, and theresulting mixture was maintained at a temperature of approximately 70°C. for 20 minutes. The resulting product was then diluted with DMF toform a red, viscous polyurethane resin/prepolymer having a 25% solidscontent and a 6% (molarity) excess of free isocyanate.

The red polyurethane resin/prepolymer solution was then directly appliedonto a commercially available silicone-treated, mirror-surface releasepaper to form a film coating having a thickness of approximately 0.15mm. Onto this coating layer a commercially available base substratehaving a thickness of 1 mm (a non-woven fibrous sheet having a thicknessof 80 microns and a polyurethane elastomer impregnated/coated andsolidified on one side) was pressed/bonded. Then, the assembly washeated to a temperature of approximately 120° C. in an oven and kept atthat temperature for 3 minutes. The assembly was then removed from theoven and cooled to room temperature, and the release paper was thenpeeled off of the assembly. A synthetic leather having a red skin layerwas thus obtained. Furthermore, no visible red color was detected on therelease paper, which suggested that none of the red colorant hadmigrated onto the release paper.

EXAMPLE 10

This example demonstrates the production of a synthetic leather articlein accordance with the invention. 116 parts (0.14 mol) of Tone® 0210polyester polyol (available from DOW) having a molecular weight of 830and an OH number of 135, 48 parts (0.04 mol) of Millijet® Red 17polymeric colorant (available from Milliken Chemical) which had beendiluted to a color value of 30 abs./g/L, 32 parts (0.36 mol) of1,4-butyleneglycol, and 374 parts of dimethylformamide (DMF) werecharged into a 3-neck flask equipped with a reflux condenser, amechanical stirrer, and a thermo-controller. With vigorous stirring, 152parts (0.61 mol) of diphenylmethane-4,4′-diisocyanate was slowly added(the [NCO]/[OH] ratio being 1.12). After stirring for 15 minutes, 300parts of DMF was added and the whole mixture was then heated toapproximately 90-100° C. for 1.5 hours to complete the reaction. Afterthe mixture had cooled to approximately 70° C., a solution containing4.2 parts (0.135 mol) of methanol in 10 parts DMF was added to themixture, and the resulting mixture was maintained at a temperature ofapproximately 70° C. for 20 minutes. The resulting product was thendiluted with DMF to form a red, viscous polyurethane resin having a 25%solids content and no excess of free isocyanate.

The red polyurethane resin/prepolymer solution was then directly appliedonto a commercially available silicone-treated, mirror-surface releasepaper to form a film coating having a thickness of approximately 0.15mm. Onto this coating layer a commercially available base substratehaving a thickness of 1 mm (a non-woven fibrous sheet having a thicknessof 80 microns and a polyurethane elastomer impregnated/coated andsolidified on one side) was pressed/bonded. Then, the assembly washeated to a temperature of approximately 120° C. in an oven and kept atthat temperature for 3 minutes. The assembly was then removed from theoven and cooled to room temperature, and the release paper was thenpeeled off of the assembly. A synthetic leather having a red skin layerwas thus obtained. Furthermore, no visible red color was detected on therelease paper, which suggested that none of the red colorant hadmigrated onto the release paper.

EXAMPLE 11

This example demonstrates the production of a synthetic leather articlein accordance with the invention. 100 parts of UR-1100 polyurethaneresin (available from Home Sun Industrial Co., Ltd of Taiwan) having aviscosity of 60,000-100,000 centipoises and a solids content of 29-31%in DMF/MEK/toluene, 10 parts of DMF, 90 parts of methyl ethyl ketone(MEK), and 0.3 parts of Millijet® Yellow 26 polymeric colorant(available from Milliken Chemical) which had been diluted to a colorvalue of 27 abs/g/L are added to a beaker. The resulting mixture wasvigorously stirred for 10 minutes using a mechanical stirrer to achievea uniform, yellow, viscous polyurethane solution. A small amount of thisyellow polyurethane solution was then directly poured onto acommercially available silicone-treated, mirror-effect release paper andspread out with a 0.12 mm-caved stainless steel drawing rod to form afilm coating having a thickness of 0.12 mm. The coated release paper wasthen placed in an oven at a temperature of approximately 120° C. Afterapproximately 1 minute, the coated release paper was then removed fromthe oven and cooled to room temperature. The coated release paper wasthen coated with a PVC forming resin solution using a 0.5 mm-caveddrawing rod to form a 0.5 mm PVC film on the surface thereof. Theresulting substrate was then placed in an oven at a temperature ofapproximately 200° C. for approximately 1 minute. After removing thecoated release paper from the oven and cooling it to room temperature,an adhesive layer measuring approximately 0.12 mm in thickness was thencoated onto the PVC film using a drawing rod. A commercially availablebase substrate (as described above) was then pressed into the freshlydeposited adhesive layer. The resulting assembly was then placed in anoven at a temperature of approximately 120° C. for approximately 1-3minutes. After the assembly had been removed from the oven and allowedto cool to room temperature, the release paper was removed. A syntheticleather article having a yellow polyurethane skin layer was thusobtained. Furthermore, no visible yellow color was detected on therelease paper, which suggests that none of the yellow polymeric coloranthad migrated onto the release paper.

COMPARATIVE EXAMPLE 1

A yellow, synthetic leather article was produced in accordance with theprocedure described in Example 11, except that the yellow polymericcolorant was replaced with 0.3 parts of a yellow dye solution (30% colorstrength of C.I. Solvent Yellow 82 in xylene). Upon removal of therelease paper, a significant amount of yellow color was observed on therelease paper. This suggests that the yellow dye had migrated onto therelease paper during the production of the synthetic leather article.

EXAMPLE 12

This example demonstrates the production of a synthetic leather articlein accordance with the invention. An orange, synthetic leather articlewas produced in accordance with the procedure described in Example 11,except that the yellow polymer colorant was replaced with 0.6 parts ofMillijet® Orange 31 polymeric colorant (available from MillikenChemical), which had been diluted to a color value of 18 abs./g/L. As inexample 11, no visible color was detected on the release paper after thesynthetic leather article had been produced, which suggests that none ofthe orange polymeric colorant had migrated onto the release paper.

COMPARATIVE EXAMPLE 2

An orange, synthetic leather article was produced in accordance with theprocedure described in Example 12, except that the orange polymericcolorant was replaced with 0.6 parts of an orange dye solution (30%color strength of C.I. Solvent Orange 54 in xylene/MEK). Upon removal ofthe release paper, a significant amount of orange color was observed onthe release paper. This suggests that the orange dye had migrated ontothe release paper during the production of the synthetic leatherarticle.

EXAMPLE 13

This example demonstrates the production of a synthetic leather articlein accordance with the invention. A red, synthetic leather article wasproduced in accordance with the procedure described in Example 11,except that the yellow polymer colorant was replaced with 0.6 parts ofMillijet® Red 17 polymeric colorant (available from Milliken Chemical),which had been diluted to a color value of 30 abs./g/L. After removingthe release paper, a slight reddish color was detected on the releasepaper, which suggests that only a trace amount of the red, polymericcolorant had migrated onto the release paper.

COMPARATIVE EXAMPLE 3

A red, synthetic leather article was produced in accordance with theprocedure described in Example 13, except that the red polymericcolorant was replaced with 0.6 parts of a red dye solution (30% colorstrength of C.I. Solvent Red 8 in xylene/MEK). Upon removal of therelease paper, a significant amount of red color was observed on therelease paper. This suggests that the red dye had migrated onto therelease paper during the production of the synthetic leather article.

EXAMPLE 14

This example demonstrates the production of a synthetic leather articlein accordance with the invention. 100 parts of UR-1100 polyurethaneresin (available from Home Sun Industrial Co., Ltd of Taiwan) having aviscosity of 60,000-100,000 centipoises and a solids content of 29-31%in DMF/MEK/toluene, 10 parts of DMF, 90 parts of methyl ethyl ketone(MEK), and 0.3 parts of Millijet® Violet 82 polymeric colorant(available from Milliken Chemical) which had been diluted to a colorvalue of 24 abs./g/L are added to a beaker. The resulting mixture wasvigorously stirred for 10 minutes using a mechanical stirrer to achievea uniform, violet, viscous polyurethane solution. A small amount of thisviolet polyurethane solution was then directly poured onto acommercially available silicone-treated, mirror-effect release paper andspread out with a 0.12 mm-caved stainless steel drawing rod to form afilm coating having a thickness of 0.12 mm. The coated release paper wasthen placed in an oven at a temperature of approximately 120° C. Afterapproximately 1 minute, the coated release paper was then removed fromthe oven and cooled to room temperature. An adhesive layer measuringapproximately 0.12 mm in thickness was then coated onto the PU filmusing the same drawing rod. A commercially available base substrate (asdescribed above) was then pressed into the freshly deposited adhesivelayer. The resulting assembly was then placed in an oven at atemperature of approximately 120° C. for approximately 1-3 minutes.After the assembly had been removed from the oven and allowed to cool toroom temperature, the release paper was removed. A synthetic leatherarticle having a violet polyurethane skin layer was thus obtained.Furthermore, no visible violet color was detected on the release paper,which suggests that none of the violet polymeric colorant had migratedonto the release paper.

EXAMPLE 15

This example demonstrates the production of a synthetic leather articlein accordance with the invention. A violet, synthetic leather articlewas produced in accordance with the procedure described in Example 11,except that the yellow polymer colorant was replaced with 0.3 parts ofMillijet® Violet 82 polymeric colorant (available from MillikenChemical), which had been diluted to a color value of 24 abs./g/L. As inexample 11, no visible color was detected on the release paper after thesynthetic leather article had been produced, which suggests that none ofthe violet polymeric colorant had migrated onto the release paper.

EXAMPLE 16

This example demonstrates the production of a synthetic leather articlein accordance with the invention. A blue, synthetic leather article wasproduced in accordance with the procedure described in Example 11,except that the yellow polymer colorant was replaced with 0.6 parts ofMillijet® Blue 28 polymeric colorant (available from Milliken Chemical),which had been diluted to a color value of 25 abs./g/L. As in example11, no visible color was detected on the release paper after thesynthetic leather article had been produced, which suggests that none ofthe blue polymeric colorant had migrated onto the release paper.

COMPARATIVE EXAMPLE 4

A blue, synthetic leather article was produced in accordance with theprocedure described in Example 16, except that the blue polymericcolorant was replaced with 0.6 parts of a blue dye solution (30% colorstrength of C.I. Solvent Blue 70 in xylene/MEK). Upon removal of therelease paper, a visible blue color was observed on the release paper.This suggests that the blue dye had migrated onto the release paperduring the production of the synthetic leather article.

EXAMPLE 17

This example demonstrates the production of a synthetic leather articlein accordance with the invention. A black, synthetic leather article wasproduced in accordance with the procedure described in Example 11,except that the yellow polymer colorant was replaced with 0.3 parts of ablack polymeric colorant. The black polymeric colorant used was obtainedby mixing 44% of Millijet® Orange 31 polymeric colorant (available fromMilliken Chemical) diluted to a color value of 18 abs./g/L, 28% ofMillijet® Violet 82 polymeric colorant (available from MillikenChemical) diluted to a color value of 24 abs./g/L, and 28% of Millijet®Blue 28 polymeric colorant (available from Milliken Chemical) diluted toa color value of 39 abs./g/L. As in example 11, no visible color wasdetected on the release paper after the synthetic leather article hadbeen produced, which suggests that none of the polymeric colorants hadmigrated onto the release paper.

COMPARATIVE EXAMPLE 5

A black, synthetic leather article was produced in accordance with theprocedure described in Example 16, except that the black polymericcolorant was replaced with 0.3 parts of a black dye solution (30% colorstrength of C.I. Solvent Black 27 in xylene/MEK). Upon removal of therelease paper, a visible black color was observed on the release paper.This suggests that the black dye had migrated onto the release paperduring the production of the synthetic leather article.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. All methodsdescribed herein can be performed in any suitable order unless otherwiseindicated herein or otherwise clearly contradicted by context. The useof any and all examples, or exemplary language (e.g., “such as”)provided herein, is intended merely to better illuminate the inventionand does not pose a limitation on the scope of the invention unlessotherwise claimed. No language in the specification should be construedas indicating any non-claimed element as essential to the practice ofthe invention.

Preferred embodiments of this invention are described herein, includingthe best mode known to the inventors for carrying out the invention.Variations of those preferred embodiments may become apparent to thoseof ordinary skill in the art upon reading the foregoing description. Theinventors expect skilled artisans to employ such variations asappropriate, and the inventors intend for the invention to be practicedotherwise than as specifically described herein. Accordingly, thisinvention includes all modifications and equivalents of the subjectmatter recited in the claims appended hereto as permitted by applicablelaw. Moreover, any combination of the above-described elements in allpossible variations thereof is encompassed by the invention unlessotherwise indicated herein or otherwise clearly contradicted by context.

1. A method for producing a synthetic leather article, the methodcomprising the step of: (a) providing a resin, (b) providing a coloredpolymer, the colored polymer comprising a product produced by reactingin a polymerization reaction a reactant mixture comprising a polymericcolorant and an isocyanate-containing compound, the polymeric colorantcomprising a chromophore and an oligomeric constituent bound to thechromophore, (c) mixing the colored polymer and the resin to form amixture, (d) applying the mixture obtained in step (c) onto a transfersubstrate and heating the substrate to dry the substrate and form aresin coating thereon, (e) applying an adhesive onto the resin coatingproduced in step (d), (f) applying a fibrous backing substrate to theadhesive layer produced in step (e), (g) heating the assembly producedin step (f) to dry the assembly and bond the fibrous backing substrateto the adhesive layer, and (h) removing the transfer substrate from theassembly produced in (g) to produce a synthetic leather article.
 2. Themethod of claim 1, wherein the polymeric colorant conforms to structure(IV)

wherein R₆ is selected from the group consisting of hydrogen, alkylgroups, aryl groups, arylalkyl groups, alkylaryl groups, and oligomericconstituents having the structure —Z—X; wherein each R₇ is independentlyselected from the group consisting of hydrogen, halogen atoms, alkylgroups, alkoxy groups, nitrile groups, nitro groups, amide groups, andsulfonamide groups, and q is an integer between 0 and 4; R₈ and R₉ areindependently selected from the group consisting of hydrogen, halogenatoms, tertiary amino groups, imine groups, cyano groups, pyridiniumgroups, ester groups, amide groups, sulfate groups, sulfonate groups,sulfide groups, sulfoxide groups, phosphine groups, phosphinium groups,phosphate groups, nitrile groups, mercapto groups, nitro groups, sulfonegroups, acyl groups, azo groups, alkyl groups, alkoxy groups, arylgroups, aryloxy groups, arylalkyl groups, arylalkoxy groups, alkylarylgroups, and alkylaryloxy groups; wherein each Z is an oligomericconstituent independently selected from the group consisting of: (i)oligomers comprising at least three monomers selected from the groupconsisting of C₂-C₂₀ alkyleneoxy groups, glycidol groups, and glycidylgroups, (ii) aliphatic oligomeric esters conforming to structure (II)

wherein R₂ and R₃ are independently selected from the group consistingof hydrogen and C₁-C₁₀ alkyl groups, f is an integer between 1 and 10,and g is any positive integer or fraction between 1 and 20, and (iii)combinations of (i) and (ii); and wherein each X is an end groupindependently selected from the group consisting of hydrogen, hydroxylgroups, thiol groups, amine groups, alkyl groups, aryl groups, alkylester groups, aryl ester groups, organic sulfonate groups, organicsulfate groups, and amide groups.
 3. The method of claim 1, wherein thepolymeric colorant conforms to structure (V)

wherein R₁₀ is selected from the group consisting of hydrogen, alkylgroups, aryl groups, arylalkyl groups, alkylaryl groups, and oligomericconstituents having the structure —Z—X; wherein each R₁₁ isindependently selected from the group consisting of hydrogen, halogenatoms, alkyl groups, alkoxy groups, nitrile groups, nitro groups, amidegroups, and sulfonamide groups, and q is an integer between 0 and 4;wherein R₁₂ is selected from the group consisting of aromatic groups andheteroatom-containing aromatic groups; wherein Q is hydrogen or alinking group selected from the group consisting of oxygen, sulfur, acarbonyl group, a sulfonyl group, a C₁-C₈ alkyl group, a C₂-C₈ alkenegroup, a p-phenylenediamine group, a m-hydroxybenzene group, and am-di(C₁-C₄) alkoxybenzene; wherein r is equal to 1 or 2; wherein each Zis an oligomeric constituent independently selected from the groupconsisting of: (i) oligomers comprising at least three monomers selectedfrom the group consisting of C₂-C₂₀ alkyleneoxy groups, glycidol groups,and glycidyl groups, (ii) aliphatic oligomeric esters conforming tostructure (II)

wherein R₂ and R₃ are independently selected from the group consistingof hydrogen and C₁-C₁₀ alkyl groups, f is an integer between 1 and 10,and g is any positive integer or fraction between 1 and 20, and (iii)combinations of (i) and (ii); and wherein each X is an end groupindependently selected from the group consisting of hydrogen, hydroxylgroups, thiol groups, amine groups, alkyl groups, aryl groups, alkylester groups, aryl ester groups, organic sulfonate groups, organicsulfate groups, and amide groups.
 4. The method of claim 1, wherein thepolymeric colorant conforms to structure (VI)

wherein R₁₃ is selected from the group consisting of hydrogen, alkylgroups, aryl groups, arylalkyl groups, alkylaryl groups, and oligomericconstituents having the structure —Z—X; wherein R₁₄ is selected from thegroup consisting of hydrogen, halogen atoms, alkyl groups, alkoxygroups, alkylamino groups, and arylamino groups; wherein R₁₅ is selectedfrom the group consisting of hydrogen, halogen atoms, alkyl groups,alkoxy groups, alkylamino groups, arylamino groups, cyano groups, nitrogroups, amide groups, sulfite groups, and sulfonamide groups; whereineach q is an integer between 0 and 4; wherein each Z is anoligomericconstituent independently selected from the group consistingof: (i) oligomers comprising at least three monomers selected from thegroup consisting of C₂-C₂₀ alkyleneoxy groups, glycidol groups, andglycidyl groups, (ii) aliphatic oligomeric esters conforming tostructure (II)

wherein R₂ and R₃ are independently selected from the group consistingof hydrogen and C₁-C₁₀ alkyl groups, f is an integer between 1 and 10,and g is any positive integer or fraction between 1 and 20, and (iii)combinations of (i) and (ii); and wherein each X is an end groupindependently selected from the group consisting of hydrogen, hydroxylgroups, thiol groups, amine groups, alkyl groups, aryl groups, alkylester groups, aryl ester groups, organic sulfonate groups, organicsulfate groups, and amide groups.
 5. The method of claim 1, wherein thepolymeric colorant conforms to structure (VII)

wherein Y is selected from the group consisting of oxygen, sulfur, and—NR₄₀, wherein R₄₀ is selected from the group consisting of hydrogen,alkyl groups, and aryl groups; wherein R₁₆ and R₁₇ are independentlyselected from the group consisting of hydrogen, halogen atoms, hydroxylgroups, alkyl groups, alkenyl groups, and alkoxy groups; wherein R₁₈,R₁₉, R₂₀, R₂₁, and R₂₂ are independently selected from the groupconsisting of hydrogen, halogen atoms, C₁-C₂₀ alkyl groups, C₁-C₂₀alkylester groups, hydroxyl groups, thio groups, cyano groups, sulfonylgroups, sulfo groups, sulfato groups, aryl groups, nitro groups,carboxyl groups, C₁-C₂₀ alkoxy groups, C₁-C₂₀ alkylamino groups,acrylamino groups, C₁-C₂₀ alkylthio groups, C₁-C₂₀ alkylsulfonyl groups,C₁-C₂₀ alkylphenyl groups, phosphonyl groups, C₁-C₂₀ alkylphosphonylgroups, C₁-C₂₀ alkoxycarbonyl groups, phenylthio groups, and oligomericconstituents having the structure -E-(Z—X)_(n); wherein at least one ofR₁₈, R₁₉, R₂₀, R₂₁, and R₂₂ is an oligomeric constituent having thestructure -E-(Z—X)_(n); wherein each Z is an oligomeric constituentindependently selected from the group consisting of: (i) oligomerscomprising at least three monomers selected from the group consisting ofC₂-C₂₀ alkyleneoxy groups, glycidol groups, and glycidyl groups, (ii)aliphatic oligomeric esters conforming to structure (II)

wherein R₂ and R₃ are independently selected from the group consistingof hydrogen and C₁-C₁₀ alkyl groups, f is an integer between 1 and 10,and g is any positive integer or fraction between 1 and 20, and (iii)combinations of (i) and (ii); and wherein each X is an end groupindependently selected from the group consisting of hydrogen, hydroxylgroups, thiol groups, amine groups, alkyl groups, aryl groups, alkylester groups, aryl ester groups, organic sulfonate groups, organicsulfate groups, and amide groups.
 6. The method of claim 1, wherein thepolymeric colorant conforms to structure (VIII)

wherein R₂₃ is selected from the group consisting of hydrogen, halogenatoms, hydroxyl groups, amine groups, nitro groups, and acetamidegroups; wherein R₂₄ and R₂₅ are independently selected from the groupconsisting of hydrogen and hydroxyl groups; wherein A is selected fromthe group consisting of alkyl groups and aryl groups; and wherein B isselected from the group consisting of groups conforming to structure(XV) and structure (XVI)

wherein R₃₈ is selected from the group consisting of hydrogen, C₁-C₁₈alkyl groups, and aryl groups; wherein R₃₉ is selected from the groupconsisting of aryl groups and oligomeric constituents having thestructure -A-Z—X; wherein each Z is an oliciomeric constituentindependently selected from the group consisting of: (i) oligomerscomprising at least three monomers selected from the group consisting ofC₂-C₂₀ alkyleneoxy groups, glycidol groups, and glycidyl groups, (ii)aliphatic oligomeric esters conforming to structure (II)

wherein R₂ and R₃ are independently selected from the group consistingof hydrogen and C₁-C₁₀ alkyl groups, f is an integer between 1 and 10,and g is any positive integer or fraction between 1 and 20, and (iii)combinations of (i) and (ii); and wherein each X is an end groupindependently selected from the group consisting of hydrogen, hydroxylgroups, thiol groups, amine groups, alkyl groups, aryl groups, alkylester groups, aryl ester groups, organic sulfonate groups, organicsulfate groups, and amide groups.
 7. The method of claim 1, wherein theresin is selected from the group consisting of polyurethane resins,polyurea resins, and combinations thereof.
 8. The method of claim 1,wherein the polymeric colorant is selected from the group of colorantsconforming to structure (I) and structure (III)

wherein R₁ or R₁-E is an organic chromophore, E is a linking moietyselected from the group consisting of nitrogen, oxygen, sulfur, asulfite group, a sulfonamide group, and a carboxyl group, and n and mare independently selected from the group consisting of integers between1 and 5; wherein R₄ or R₄(G)_(h) is an organic chromophore, G isselected from the group consisting of SO₃ ³¹ and CO₂ ³¹, each R₅ isindependently selected from the group consisting of hydrogen, alkylgroups, and aryl groups, M is selected from the group consisting ofnitrogen atoms and phosphorous atoms, h is an integer between 1 and 4, kis an integer between 0 and 5, j is an integer between 1 and 6, and thesum of k and j is equal to 4 when M is a nitrogen atom and 6 when M is aphosphorous atom; wherein each Z is an oligomeric constituentindependently selected from the group consisting of: (i) oligomerscomprising at least three monomers selected from the group consisting ofC₂-C₂₀ alkyleneoxy groups, glycidol groups, and glycidyl groups, (ii)aliphatic oligomeric esters conforming to structure (II)

wherein R₂ and R₃ are independently selected from the group consistingof hydrogen and C₁-C₁₀ alkyl groups, f is an integer between 1 and 10,and g is any positive integer or fraction between 1 and 20, and (iii)combinations of (i) and (ii); wherein each X is an end groupindependently selected from the group consisting of hydrogen, hydroxylgroups, thiol groups, amine groups, alkyl groups, aryl groups, alkylester groups, aryl ester groups, organic sulfonate groups, organicsulfate groups, and amide groups.
 9. The method of claim 1, wherein thesubstrate is a textile material selected from the group consisting ofwoven textiles, knit textiles, and non-wovens.